Office



- cmnrou ELLIS, or monromm, NEWJERSEY, Assren oR r ELLIS-FOSTER oomranxl 4 "'AOORPORATIONOFNEWJERSEYP"' 'nmounr am) rnoosss OF MAKING 9 Ho Drawing.-

To all whom it may concern: p Be it known that I, CARLETON ELLIS, a icitizen of the United States, and a resident of Montclair, in the county of Essex and State .of New Jersey, have invented certain new and useful Improvements in Briquets and Processes of Making Same, of which the following is a specification.

This invention relates to making briquets 10 by the use ofa bindin agent and relates particularly to the use 0 a'binding composition or an adhesive formed by the solution of sulfite cellulose Waste liquor solids in water or other aqueous medium, such solids being preferably produced in a' dry pulverulent form, as by drying by atomization, and preferably these solids show an acid reaction; thus giving to the solution prepared therefrom a similar aci'dreaction, which solution of course, may be rendered of any degree of acidity or alkalinity by the addition of suitable bodies; In the follow-- ing descriptionthe preparation of the S111- fite liquor and certain of its applications, as for example, in the manufacture of briquets are set forth.

Sulfite waste. liquor in 'a concentrated or solid form has beenproposed as a binding material for briquets and the like, but being 3.0 soluble in water briquets made from it will.- not stand the action, of wet weather as when exposed to rain inf-open carsduring transportation. Pitch. andtar have been suggested as waterproofingagents for the sulfite liquor but owing to the smoke and soot produced by these there is little likelihood of general acceptance of binders of this character;

Many attempts' have been made -torender ilsulfite liquor waterproof but so far as'I know, no satisfactory method to this end formaking briquetsand plastics has been devised. s V

I have found that the concentrated liquor, t5 especially the more acid types of-the sulfite waste liquor, are capable .of beingprecipL- tated b lime to form asubstantially insoluble ody, so far as this art is concerned, and which enable briquets to be prepared which resist the disintegrating effects of' water to the degree desired. It is of course, somewhat remarkable that sulfite waste liquor .eonsisting so lar ely of lime compounds, should be precipltated by quicklime' or hydrated lime,-but such is the case,- espe- Specification or Ietters' Patent. Application f led August 16, 1917, serial No.'186,4 81.

- crushed rock, sand, fiber,

' Patented July 29, 1.919.

' cially with the slightly acid varieties of the liquor. The liquors obtained from raw materials contaming a rather high percentage of magnesia are preferable.

The product may be used for making flooring compounds, artificial stone, columns, and all sorts of plastics, as will now'be evident.

In carrying out the method I may for example, take sulfite liquor preferably of an acid character, such as maybe made-by conoentrating in an acid condition or partially neutralized state, or by acidifying the neutral concentrate. Ido not mean'to exclude the 'neutral or alkaline, or hydrolyzed, or

other forms or derivatives of. sulfite waste liquor or spruce or other cellulose liquors of a substantially equivalent character from the viewpoint of the present invention. The

liquor is mixed with the materials to be bound together as coal dust or fines, culm, sawdust, mineral; fillers, talc,

asbestos, and the like, and then caustic lime ina finely divided condition may be admixed therewith. Reaction takes place almost immediately with some liquors and the insoluble compound is formed in and around the filling material. Sometimes the reaction is not immediate, especially when the sulfite liquor is diluted with 20 to 50% of water, or when the sulfite magnesite,

liquor solids are because of the nature of the concentration in a less unstable condition.- Thus in various ways, the setting time may be controlled so that opportunity is afforded to work the plastic into suitable shape after mixing. Hydrated lime works usually a little slower than quick-lime. About 50% of lime reckoned on the weight of sulfite liquor of 30 B. is a satisfactory'amoimt of precipitant. 30% and even less will serve but the setting time is greatly protracted, which of course, for some purposes, may not be undesirable. From 30-50% isfhoweve'r recommended for general operation; This may be exceeded in some cases. 4 a

In preparing a briquet from culm or coal material of various sorts the sulfite liquor may be mixed With this material ito uniformly coat the particles thereof and the lime in fine powder may then be admixed, or the coal may first be floured with the lime and the sulfite liquor then added and thor;

oughly incorporated, briqueting following as soon as possible. Or the lime may be added in the form of the hydrate, or as a paste or and so forth. The coal particles need not -ingto-a-strong spray of water 5 owed a action under the circumstances.

*dles,

as milk or cream of lime. To secure the best results briqueting or forming into shape should take place before material setting has occurred.

The action of the lime or other precipitant employed is that of trueprecipitation or coagulation, as the product in its preferred form is unattacked by boiling water although the sulfite liquor in the acld form 10 preferably used is readily soluble in cold water.. i v

On the weight of the coal employed from '6 to 10 per cent. of sulfite liquor maybe used, the proportion varying between these or other limitsaccording to the character of the coal, amount of briqueting pressure,

be uniformly coated with the sulfite liquor provided'suilicient of thelatter be present to secure the required bonding effect.

Tests made with such .briquetsqby exposplain sulfite'liquor briquet to fall to pieces -in tenminutes while the limed-product resisted perfectly for a period of four hours when the test was discontinued.

Although the reaction takes place readily in the cold with the lime reagent as above, heat may beemployed if desired to mod fy the reaction. When precipitants otherthan lime are used the conditions should .be adjusted to meet any modification of the re- Similarly although the process is described more particularly with referenceto the production of briquets it will now be evident that the reaction may be applied to other fields where it is desired to precipitate sulfite liquor to yield an insoluble product, especially as distinguished from salting out procedures known in the art. Thus flooring, tool hanblocks, andQall kinds of molded prod ucts may be obtained. Added to paper stock in the beater engine,

giving a sizing material which serves for some of the darker paper, at least, and such size may be used in conjunction with rosin or other size if .50

desired.

' t For convement shipment and for certain other reasons including readiness with which the material may be incorporated with the. coal or similar stock, the sulfite liquor may be dried to a solid'and ground to a powder which yields the materiallin a pulveru'lent condition. This powder is then. mixed with the coal, lime, being added before or after or with such mixture, and waterrincorporated so as to cause the reaction either in the bulk mass or after forminginto briquets.

Similarly a pulverulent product consist- I ing of a mixture of the dry sulfite liquor solids and hydrated lime may be prepared for use as a binder.

the sulfite liquor solids may be thrown down with lime or similar precipitant,

shades of Other precipitants than lime may be employed as stated. Preferably however; a

basic body such as lime or barium hydrate; is I recommended and preferably with the acidsulfite cellulose waste liquor, it being desir able to have only a moderate degree of acidity to permit of'the reaction taking place with effectiveness.

Barium hydrate is not aspowerful a precipitant as calcium hydrate, 'on some liquors. Lime 1s aspecific preclpltant. Another con sideration is that in the case of briquets it becomes'necessary to consider the ash of the fuel. Anyi addition of sulfur compounds. such aspyrite is of course regarded as obas it softens the clinker rendering same less likely to freeze to the stove fire box' or grates. With 6% of sulfite liquor and 3% of lime the resulting ash is not objectionable in the case ofmostgrades'ofcoal, both anthracite and bituminous.

It has been noted byPollacsek (-Gernian- Patent 100,550) that sulfite Waste liquor could'be used asfa binding material for making briquets but that the'application of concentrated sulfite waste liquor in this manner a had certain disadvantages, among which was the cost of concentration. fore made use of the crude cellulose sulfite waste liquor without any treatment whatsoever, and. claimed the advantage of elim-i- He therenating the cost of concentration and of puri fication. He states that he uses the crude liquor without any purification, which is mixed with fragments of coal or turf, with magnesia. He recommends 1 part of the crude liquor to 5 parts of coal fragments, to

which'is added about 1% of quick lime and magnesia,'calculated on the weight of the mixture. There isno suggestion by him of carrying out the operation to produce a coagulated sulfite liquor acting as a waterproof or weather-proof binder and furthermore there is the disadvantage in his method that the treatment of more or less porousmaterial withthe liquor in its crude state causes a considerable amount to be taken up by capillary spacesand rendered vuseless at the surfaces where binding is required, so that the binding eflect is not satthe addition of a small amount of lime and isfactory as it should be. Another point is that the crude sulfite waste liquor con- 'tains acid material including sulfurous acid, which if not completely neutralized by the -l1me employed would tend to oxidise to so A jectionable, while lime is even advantageous r the material so as to act as a binder ciency. f In the' prooessof concen .ltration the T free sulfurous jaeid' 1s expelledder fsuchf 'condition's a; form; :jof the sulfite ia dtymy' method aw as djcated'la v n re ened'form, a subof any acids or wastef'liquor solids obtained' hvliichl is readily coaguableiand more effective than the stable isolids of the crude product. -:The' usejof or--v-;so off'lime based on the amount; of the ;:concentrated" cellulose liquor femployed-qin' the briquet enablesa neutralto alkalin reaction to be obtained so that the equilibrinm; of the acid composition 1supsetflanda satisfactory precipitation and coagn'lation-- of the solids ensues. in the bri quet.

' Avery satisfactoi'y method oi -freeing the. .sulfite liquor from free sulfurous acid is that;

of concentrating a thinsyrup in a vac 1n atomizing the syrup warhea air "to but which reactsinthepresence of moisture and heat especially when renderedalkaline product *such as is referred to 'above'. A

l material with coal fragments a'dding 'water "and.asmallamountof'hydratb of lime tosep of such dried cellulose cure an alkalinereaction, briqueting and -heating to formiasolubh'product, and one feature of the present invention-is the use ,t agent suchas coal "fragments, iron oreor other mineral matten and the. like 't'o form' a molded mass suchasa briquet' and. ;il1"inso'lubilizing the binding agentto reduce a substantially waterproof .or west er-proof mass capable of resisting the efiect of weather and moisture under such conditions as would normally be required of fuel briquets' and the-like.

der or granular fragmental'- mat As I have stated in Serial ,No. 779,516 renewed as Serial No. 239,882 ,waste sulfite cellulose liquor solids in the form otra powm paste form may be prepared in such condition as to be readily soluble in water so that the dried stock material may be reduced or dissolved in water to make'a solution of the desired density and viscosity at the time of use. The concentrated sulfite cellulose liquor of, say, a gravity of 30 Be, as such is a fairlyh-stable composition progresses 1111 uum pan or any other. suitable manner and sulfite' waste liquor- 1 solid in-combinationgwith a. bulking ial or but being dried to a solid material such 'asv a powder, is likely to undergo undesirablechanges which would render it insoluble or prone to become insoluble in. storage. By

employingthe method described herein a frag-v such,

productis obtained which is of a dry, mental or pulverulent character of stability, that it may be packed in slack cooperage, such asbfloor'barrels which are pervious toair and'in this condition may be stored in such air-pervious packages for an product is used which-shows quite a marked resistance to atmospheric influences, as for.

example, when a .fine powder of ordinary dried solids of sulfite liquor prepared according to the pnocessesheretofore proposed, is 'exposed in thin layers to air, in a short time ittends to become rather sticky and gummy, whilein the present case the pulveruhent material in the preferred form is more resistant under like test and yet is of a Qsufiiciently-unstable nature to be suitably coagailated when heatel in a briquct under normal coagulating condi tions.

Solutions of the dry Slllfite liquor solids p jmay be readily made by dissolv ng these byliine and the like to form a coagulated solids in'water to produce solutions of anydesired strength, such for example, as, a

syrup composition of 25430? B. containing say, 30-50% of solid material and in v place ofwater as a solvent aqueous media ofvarious kinds, such as saline solutions and as may be desired 7 The addition to the sulfite liquor of a comthe likemay be employed to such an extent pound such as silicate of soda may be made to assist in the binding action and in the coagulation by heating. The change in the composition'of the suliiteliquor material by the addition of silicate of soda usually is not immediate at. first but on standing reaction takes place and especially-if the material is used in a briquet the coagulating and bindingcifect becomes quite apparent. The addition of 10 to 15% of etroleum oil such as 'asphaltic' oil may also e made along with the sulfite liquor in preparing a waterproof briquet and even in some'cases 3 to 5% of oil may be employed and 1% or so of cal-' cium stearate.

f In the manufacture of briquets from culm or similar mineralmaterial the dr binder of the character particularly speci 'ed may be merely incorporated with theddry material and the mixture afterward wetted and pressed into shape. In the preferred form of the invention a solid binder is employed and this material is characterized in that a solution thereof has considerably less viscosi ity, usually from 10 to 50% less viscosity than ordinary sulfite' cellulose waste liquorwhich has been merely concentrated to that point without having previously been dried and then diluted with water. Hence there is an advantage in some cases in concentrating rial No. 757,301 now Patent No. 1,246,805, filed March 28, 1913, Nov. 13, 1917 What I claim is i 1. A process of making shaped articles,

which comprises incorporating dried pulverulent sulfite waste sulfite liquor solids, an agent capable of insolubilizing thesame, a waterproofing agent, water, and a material to serve as a filler, and shaping the mass.

2. A process of making shaped articles,.which comprises .incorporatin dried,

- slightly oxidized, atomized, pulveru ent sulsome cases briquets or other products pre-' pared from such dried solids of the sulfite waste liquor of less viscosity show fewer hair lines or cracks and reater resistance at atmospheric or mechanical erosion.

From the foregoing it will be readily understood that, by the concentration of waste sulfite liquor, the product is rendered substantially free from sulfurous acid so that the action of sulfurous acid on the added lime'is avoided, and sulfur, which is objectionablesin briquets, is reduced to a minimum. It will also be readily understood from the foregoing description that, by reason of the chemical reactions which take place during concentration, the constituents of the sulfite liquor which are better acted upon by a reagent such 'as lime, in my process, are in a chemically unstable condltion as compared with their condition in unconcentrated sulfite liquor so that, upon the addition of limethe desired reactions take place in an efi'ective manner, especially when the mass is heated.

The present application is in art a continuation of my copending app ication Sefite waste sulfite liquor solids, an agent capable of insolubilizing the same, a waterproofing agent,'water, and a material to serve as a filler, and shaping the mass.

3. A process of making shaped articles, which comprises incorporating dried, pulverulent sulfite waste sulfite liquor solids, an agent capable of insolublizing the same, a waterproofing agent, water, and fine fuel, and shaping the mass.

' 4. In the production of shaped products containing sulfite waste liquor acid solids, the step of adding an agent capable of insolubilizing the said liquor solidsandan oil in amount suiiicient to at least partially water-proof the product.

5. The process of making briquet fuel which comprises drying sulfite waste liquor in an acid state, then reducin the. product to a powder, adding an aspha tic oil thereto, mixing such product with fine coal material, and a calcareous material, moistening and shaping the mass and heating to render the sulfite liquor solids insoluble in Water.

CARLETQN' ELLIS. 

